Mono- and bis-azo compounds containing 6-hydroxy-3-heterocyclic onium-pyridone-2-groupings coupled to diazo components containing diazine or triazine rings

ABSTRACT

Reactive dyes of the formula ##STR1## where n is 1 or 2, 
     X is a six-membered halogen-containing nitrogen heterocycle, 
     L 1 , depending on n, is fluorine, chlorine, C 1  -C 4  -alkoxy, phenoxy, C 1  -C 4  -alkyl, substituted or unsubstituted phenyl or a bridge member which has one or two hydroxysulfonyl groups, 
     D is the radical of a diazo component of the aniline or naphthalene series which has at least one hydroxysulfonyl group, 
     L 2  is hydrogen or substituted or unsubstituted C 1  -C 8  -alkyl, 
     L 3  is the cationic radical of an aromatic heterocycle which is linked to the pyridone ring via a nitrogen atom, and 
     L 4  is hydrogen or C 1  -C 4  -alkyl, 
     with the proviso that the number of hydroxysulfonyl groups in the molecule exceeds that of the cationic groups by at least one, are useful for dyeing and printing hydroxyl- or nitrogen-containing substrates.

The present invention relates to novel reactive dyes of the formula I ##STR2## where n is 1 or 2,

X in case a), when n is 1, is a radical of the formula IIa, IIb or IIc ##STR3## where R¹ is hydrogen or C₁ -C₄ -alkyl and Hal fluorine or chlorine, or in case b), when n is 2, is a radical of the above-mentioned formula IIa,

L¹ in case a), when n is 1 and X is a radical of the formula IIb or IIc, is fluorine, chlorine, C₁ -C₄ -alkoxy or phenoxy, in case b), when n is 1 and X is a radical of the formula IIa, is C₁ -C₄ -alkyl or phenyl which may be monosubstituted or disubstituted by hydroxysulfonyl, or vinylsulfonyl or the radical

    --SO.sub.2 --C.sub.2 H.sub.4 --Z,

where Z is a group which is detachable under alkaline reaction conditions, or in case c), when n is 2 and X is a radical of the formula IIa, is a bridge member which has one or two hydroxysulfonyl groups,

D is the radical of a diazo component of the aniline or aminonaphthalene series which has at least one

hydroxysulfonyl group,

L² is hydrogen or C₁ -C₈ -alkyl which may be hydroxyl-substituted and interrupted by one or two oxygen atoms in ether function,

L³ is the cationic radical of a five- or six-membered aromatic heterocycle which has at least one nitrogen atom with or without one or two further hetero atoms selected from the group consisting of nitrogen, oxygen and sulfur and which is linked to the pyridone ring via the nitrogen atom, and

L⁴ is hydrogen or C₁ -C₄ -alkyl, with the proviso that the number of hydroxysulfonyl groups in the molecule exceeds that of the cationic groups by at least one, and also to the use of the novel dyes for dyeing or printing hydroxyl- or nitrogen-containing substrates.

DE-A-2 752 282 and U.S. Pat. No. 4 673 735 disclose basic azo dyes whose coupling components are derived from hydroxypyridones which inter alia contain a pyridinium radical.

It is an object of the present invention to provide novel azo-based reactive dyes which are likewise derived from a hydroxypyridone derivative having a cationic heterocyclic radical. The novel dyes shall have good wet and light fastness properties in use.

We have found that this object is achieved by the reactive dyes of the formula I defined at the beginning.

Any alkyl appearing in the abovementioned formula I may be-either straight-chain or branched.

L², L⁴ and R¹ are each for example methyl, ethyl, propyl, isopropyl, butyl, isobutyl or sec-butyl.

L² may also be for example pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, 2-methylpentyl, heptyl, 2-methylhexyl, octyl, 2-methylheptyl, 2-ethylhexyl, 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-isopropoxyethyl, 2-butoxyethyl, 2- or 3-methoxy-propyl, 2- or 3-ethoxypropyl, 2- or 3-propoxypropyl, 2- or 3-butoxypropyl, 2- or 4-methoxybutyl, 2- or 4-ethoxybutyl, 2- or 4-propoxybutyl-, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 4,8-dioxanonyl, 3,7-dioxaoctyl, 3,7-dioxanonyl, 4,7-dioxaoctyl, 4,7-dioxanonyl, 2- or 4-butoxybutyl, 4,8-dioxadecyl, 2-hydroxyethyl, 2- or 3-hydroxypropyl, 2- or 4-hydroxybutyl, 5-hydroxy-3-oxapentyl, 6-hydroxy-4-oxahexyl, 8-hydroxy-4-oxaoctyl or 9-hydroxy-4,7-dioxanonyl.

In case a), when n is 1 and X is a radical of the formula IIb or IIc, L¹ is for example methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy or sec-butoxy.

In case b), when n is 1 and X is a radical of the formula IIa, L¹ is for example methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, phenyl, 2-, 3- or 4-hydroxysulfonylphenyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dihydroxysulfonylphenyl, 2-, 3- or 4-vinylsulfonylphenyl or a radical of the formula ##STR4## Here Z is a group which is detachable under alkaline reaction conditions. Such groups are for example chlorine, bromine, C₁ -C₄ -alkylsulfonyl, phenylsulfonyl, OSO₃ H, SSO₃ H, OP(O)(OH)₂, C₁ -C₄ -alkylsulfonyloxy, substituted or unsubstituted phenylsulfonyloxy, C₁ -C₄ -alkanoyloxy, C₁ -C₄ -dialkylamino or a radical of the formula ##STR5## where Q¹, Q² and Q³ are identical or different and each is independently of the others C₁ -C₄ -alkyl or benzyl, and An.sup.⊖ is in each case an anion. Suitable anions An.sup.⊖ are for example fluoride, chloride, bromide, iodide, mono-, di- or trichloroacetate, methanesulfonate, benzenesulfonate or 2- or 4-methylbenzenesulfonate.

In case c), when n is 2 and X is a radical of the formula IIa, L¹ is a bridge member which has one or two hydroxysulfonyl groups.

Suitable bridge members are for example mono- or dihydroxysulfonylphenylene, such as 4-hydroxysulfonyl-1,2-phenylene or 2,5-dihydroxysulfonyl-1,4-phenylene, mono- or dihydroxysulfonylbiphenylene, such as 2-hydroxysulfonyl-4,4,-biphenylene or 2,2'-dihydroxysulfonyl-4,4'-biphenylene, mono- or dihydroxysulfonylstilbenediyl, such as ##STR6## or mono- or dihydroxysulfonyl-4,4'-ureylenebisphenyl, such as ##STR7##

D is derived for example from diazo components of the aniline or aminonaphthalene series which have at least one, preferably one or two, hydroxysulfonyl groups as substituents.

Examples are the following diazo components L⁴ --NH--D--NH₂, where L⁴ is in each case as defined above: ##STR8##

Suitable heterocycles from which the radical L³ is derived belong for example to the class of the pyrroles, pyrazoles, imidazoles, oxazoles, isoxazoles, thiazoles, isothiazoles, triazoles, oxadiazoles, thiadiazoles, pyridines, pyridazines, pyrimidines or pyrazines. These radicals may be substituted for example by C₁ -C₁₈ -alkyl, in particular C₁ -C₄ -alkyl, or carboxyl.

Of special interest are heterocycles of the class of the imidazoles or pyridines. Radicals L³ derived from such heterocycles conform in particular to the formula ##STR9## where R², R⁴ and R⁵ are identical or different and each is independently of the others hydrogen or C₁ -C₄ -alkyl, and R³ is hydrogen or C₁ -C₁₈ -alkyl, in particular C₁ -C₄ -alkyl.

The reactive dyes of the formula I are customarily present in the form of inner salts, so that, if the cationic heterocyclic radical L³ contains for example a carboxyl group, the counter-ion is a carboxylate anion; in all other cases the counter-ion is a sulfonate anion.

Preference is given to reactive dyes of the formula I where X is a radical of the formula IIa or IIb and L¹ in case a), when n is 1 and X is a radical of the formula IIb, is chlorine, in case b), when n is 1 and X is a radical of the formula IIa, is C₁ -C₄ -alkyl or phenyl which may be monosubstituted or disubstituted by hydroxysulfonyl, vinylsulfonyl or the radical --SO₂ --C₂ H₄ --Z, where Z is a group which is detachable under alkaline reaction conditions, or in case c), when n is 2 and X is a radical of the formula IIa, is a bridge member which has one or two hydroxysulfonyl groups.

Preference is further given to reactive dyes of the formula I where D is the radical of a diazo component of the aniline series which has one or two hydroxysulfonyl groups.

Particular preference is given to reactive dyes of the formula Ia ##STR10## where n, R¹, Hal, L³ and L⁴ are each as defined above,

L² is hydrogen or C₁ -C₄ -alkyl,

A is hydrogen or hydroxysulfonyl, and

L¹, when n is 1, is C₁ -C₄ -alkyl or phenyl which may be monosubstituted or disubstituted by hydroxysulfonyl, vinylsulfonyl or the radical --SO₂ --C₂ H₄ --Z, where Z is a group which is detachable under alkaline reaction conditions, or, when n is 2, is mono- or dihydroxysulfonylphenylene, mono- or dihydroxysulfonylbiphenylene, mono- or dihydroxysulfonylstilbenediyl or mono- or dihydroxysulfonyl-4,4'-ureylenebisphenyl.

Of particular interest are reactive dyes of the formula Ia where L³ is the cationic radical of a heterocycle of the imidazole or pyridine series which is attached to the pyridone ring via the nitrogen atom.

Of particular suitability are reactive dyes of the formula Ia where L³ is the radical of the formula ##STR11## where R², R³, R⁴ and R⁵ are each independently of the others hydrogen or C₁ -C₄ -alkyl.

The reactive dyes of the formula I according to the present invention can be prepared in a conventional manner.

For example, a diazo component of the formula III

    L.sup.4 --NH--D--NH.sub.2                                  (III),

where L⁴ and D are each as defined above, can be reacted with a haloheterocycle of the formula IVa or IVb ##STR12## where Hal is fluorine or chlorine, and the resulting condensation product of the formula Va or Vb ##STR13## where Hal, L⁴ and D are each as defined above, reacted with a C₁ -C₄ -alkanol, phenol or an amine of the formula VI

    L.sup.1 (--NH--R.sup.1).sub.n                              (VI),

where L¹, R¹ and n are each as defined above. Depending on n, a molar ratio of condensation product Va/Vb: amine VI of about 1:1 or 2:1 should be maintained here.

The resulting intermediate of the formula VII ##STR14## where L¹, X, L⁴, D and n are each as defined above, is then diazotized and coupled with a pyridone of the formula VIII ##STR15## where L² and L³ are each as defined above and An.sup.⊖ is one equivalent of an anion, for example halide, such as chloride, bromide or iodide, or sulfate. (If L³ is derived from a pyridinecarboxylic acid, there is of course no external anion An.sup.⊖ present, since in this case the radical L³, as mentioned earlier, is present in the form of an inner salt.)

It is also possible to diazotize the condensation product Va or Vb and to couple its diazonium product with the pyridone VIII to form the reactive dyes of the formula Ib or Ic ##STR16## where Hal, L⁴, D, L² and L³ are each as defined above. These reactive dyes may then be additionally reacted with an amine of the formula VI.

The novel reactive dyes of the formula I are advantageously suitable for dyeing or printing hydroxyl-or nitrogen-containing organic substrates. Such substrates are for example leather or fiber materials which predominantly contains natural or synthetic polyamides or natural or regenerated cellulose. The novel dyes are preferably suitable for dyeing or printing textile material based on wool or in particular cotton.

The dyes of the present invention produce brilliant greenish yellow to reddish yellow dyeings which have a high light fastness and good wet fastness properties, in particular a high peroxide wash fastness and a high peroxide bleach fastness.

The examples which follow further illustrate the invention.

EXAMPLE 1

25.3 g (0.1 mol) of aniline-2,5-disulfonic acid were dissolved in 200 ml of water at pH 7 and admixed at 0° C. with a suspension of 18.5 g (0.1 mol) of cyanuric chloride in 250 ml of ice-water. Sodium bicarbonate was added to maintain a pH of from 6 to 7 at from 0° to 5° C. for 2 hours.

When free amino groups were no longer detectable, the mixture was filtered and the filtrate was admixed with a neutral solution of 18.8 g (0.1 mol) of 1,3-diaminobenzene-4-sulfonic acid in 200 ml of water. The reaction was then stirred at 15°-20° C. and pH 6-7 until it had ended, as detected by thin layer chromatography. The secondary condensation product thus obtained was diazotized in the presence of hydrochloric acid at 0°-5° C. and admixed with 24.2 g of 3-(3-methylimidazol-1-ylium)-4-methyl-6-hydroxypyrid-2-one hydrochloride. Sodium bicarbonate was added to complete the coupling at pH 6-7. Sodium chloride was added to salt out the dye of the formula ##STR17## It dyes cotton in a brilliant greenish yellow shade having a good light fastness and good wet fastness properties, in particular good peroxide wash and bleach fastness properties.

EXAMPLE 2

55.3 g (0.1 mol) of the secondary condensation product of 1,3-diaminobenzene-4,6-disulfonic acid, cyanuric chloride and aniline-4-sulfonic acid were diazotized in 600 ml of ice-water in the presence of hydrochloric acid and admixed with 24.2 g (0.1 mol) of 3-(3-methylimidizol-1-ylium)-4-methyl-6-hydroxypyrid-2-one hydrochloride. Sodium bicarbonate was added to complete the coupling at pH 6-7, and the dye formed was precipitated with sodium chloride. It conforms to the formula ##STR18## and dyes cotton in a brilliant greenish yellow shade having a good light fastness and good wet fastness properties, in particular good peroxide wash and bleach fastness properties.

The method of Examples 1 and 2 is also used to obtain the Examples of Table 1.

                                      TABLE 1                                      __________________________________________________________________________      ##STR19##                                                                     Example                                         Hue on                         No.  Y.sup.1              Hal                                                                               A   Y.sup.2                                                                            Y.sup.3    cotton                         __________________________________________________________________________      3                                                                                   ##STR20##           Cl H   H                                                                                   ##STR21## Greenish yellow                 4                                                                                   ##STR22##           F  H   H                                                                                   ##STR23## Greenish yellow                 5                                                                                   ##STR24##           Cl H   H                                                                                   ##STR25## Greenish yellow                 6                                                                                   ##STR26##           Cl H   H                                                                                   ##STR27## Greenish yellow                 7                                                                                   ##STR28##           Cl SO.sub.3 H                                                                         H                                                                                   ##STR29## Greenish yellow                 8                                                                                   ##STR30##           Cl SO.sub.3 H                                                                         H                                                                                   ##STR31## Greenish yellow                 9                                                                                   ##STR32##           F  H   H                                                                                   ##STR33## Greenish yellow                10                                                                                   ##STR34##           Cl H   CH.sub.3                                                                            ##STR35## Greenish yellow                11                                                                                   ##STR36##           Cl H   CH.sub.3                                                                            ##STR37## Greenish yellow                12                                                                                   ##STR38##           Cl SO.sub.3 H                                                                         CH.sub.3                                                                            ##STR39## Greenish yellow                13                                                                                   ##STR40##           Cl SO.sub.3 H                                                                         CH.sub.3                                                                            ##STR41## Greenish yellow                14                                                                                   ##STR42##           Cl SO.sub.3 H                                                                         CH.sub.3                                                                            ##STR43## Greenish yellow                15                                                                                   ##STR44##           Cl H   C.sub.2 H.sub.5                                                                     ##STR45## Greenish yellow                16                                                                                   ##STR46##           Cl H   C.sub.2 H.sub.5                                                                     ##STR47## Greenish yellow                17                                                                                   ##STR48##           Cl SO.sub.3 H                                                                         C.sub.2 H.sub.5                                                                     ##STR49## Greenish yellow                18                                                                                   ##STR50##           Cl SO.sub.3 H                                                                         C.sub.2 H.sub.5                                                                     ##STR51## Greenish yellow                19                                                                                   ##STR52##           Cl SO.sub.3 H                                                                         C.sub.2 H.sub.5                                                                     ##STR53## Greenish yellow                20   Cl                   Cl SO.sub.3 H                                                                         H                                                                                   ##STR54## Greenish yellow                21                                                                                   ##STR55##           Cl SO.sub.3 H                                                                         H                                                                                   ##STR56## Greenish yellow                22                                                                                   ##STR57##           Cl SO.sub.3 H                                                                         H                                                                                   ##STR58## Greenish yellow                23                                                                                   ##STR59##           Cl SO.sub.3 H                                                                         H                                                                                   ##STR60## Greenish yellow                24                                                                                   ##STR61##           Cl H   H                                                                                   ##STR62## Greenish yellow                25                                                                                   ##STR63##           Cl H   H                                                                                   ##STR64## Greenish yellow                26                                                                                   ##STR65##           Cl H   H                                                                                   ##STR66## Greenish yellow                27                                                                                   ##STR67##           Cl H   H                                                                                   ##STR68## Greenish yellow                28                                                                                   ##STR69##           Cl H   H                                                                                   ##STR70## Greenish yellow                29                                                                                   ##STR71##           Cl SO.sub.3 H                                                                         H                                                                                   ##STR72## Greenish yellow                30                                                                                   ##STR73##           Cl H   H                                                                                   ##STR74## Greenish yellow                31                                                                                   ##STR75##           F  H   H                                                                                   ##STR76## Greenish yellow                32                                                                                   ##STR77##           Cl SO.sub.3 H                                                                         H                                                                                   ##STR78## Greenish yellow                33                                                                                   ##STR79##           Cl SO.sub.3 H                                                                         H                                                                                   ##STR80## Greenish yellow                __________________________________________________________________________

EXAMPLE 34

33.6 g (0.1 mol) of the condensation product of 1,3-diaminobenzene-4-sulfonic acid and cyanuric chloride were stirred in 500 ml of ice-water at pH 6-7 and 30°-35° C. with 10.1 g (0.05 mol) of 1-amino-3-methylaminobenzene-4-sulfonic acid until the reaction had ended, as detected by thin layer chromatography. This was followed by a diazotization in the presence of hydrochloric acid and the addition of 24.2 g of 3-(3-methylimidazol-1-ylium)-4-methyl-6-hydroxypyrid-2-one hydrochloride. Sodium bicarbonate was added to complete the coupling at pH 6-7. The dye obtained conforms to the formula ##STR81## It was precipitated with sodium chloride and dyes cotton in a greenish yellow shade having a good light fastness and good wet fastness properties.

The method of Example 34 is also used to obtain the dyes listed in Table 2.

                                      TABLE 2                                      __________________________________________________________________________      ##STR82##                                                                     Example                                          Hue on                        No.  L.sup.1                Hal                                                                               A   L.sup.2                                                                           L.sup.3    cotton                        __________________________________________________________________________     35                                                                                   ##STR83##             Cl SO.sub.3 H                                                                         H                                                                                  ##STR84## Greenish yellow               36                                                                                   ##STR85##             Cl H   H                                                                                  ##STR86## Greenish yellow               37                                                                                   ##STR87##             Cl SO.sub. 3 H                                                                        H                                                                                  ##STR88## Greenish yellow               38                                                                                   ##STR89##             Cl H   H                                                                                  ##STR90## Greenish yellow               39                                                                                   ##STR91##             Cl SO.sub.3 H                                                                         H                                                                                  ##STR92## Greenish yellow               40                                                                                   ##STR93##             Cl H   H                                                                                  ##STR94## Greenish yellow               41                                                                                   ##STR95##             Cl SO.sub.3 H                                                                         H                                                                                  ##STR96## Greenish yellow               42                                                                                   ##STR97##             Cl H   H                                                                                  ##STR98## Greenish yellow               43                                                                                   ##STR99##             Cl SO.sub.3 H                                                                         H                                                                                  ##STR100##                                                                               Greenish yellow               44                                                                                   ##STR101##            Cl H   H                                                                                  ##STR102##                                                                               Greenish yellow               __________________________________________________________________________

EXAMPLE 45

Example 1 was repeated, except that the 1,3-diaminobenzene-4-sulfonic acid was replaced by 1,4-diaminobenzene-2-sulfonic acid, affording, after salting out with sodium chloride, the dye of the formula ##STR103## It dyes cotton in a reddish yellow shade having a good light fastness and good wet fastness properties.

The method of Example 2 is also used to obtain the dyes listed in Table 3.

                                      TABLE 3                                      __________________________________________________________________________      ##STR104##                                                                    Example                                Hue on                                  No.  L.sup.1      Hal                                                                               A   L.sup.2                                                                           L.sup.3    cotton                                  __________________________________________________________________________     46                                                                                   ##STR105##  Cl H   H                                                                                  ##STR106##                                                                               Reddish yellow                          47                                                                                   ##STR107##  Cl SO.sub.3 H                                                                         H                                                                                  ##STR108##                                                                               Reddish yellow                           48                                                                                  ##STR109##  Cl SO.sub.3 H                                                                         H                                                                                  ##STR110##                                                                               Reddish yellow                          49                                                                                   ##STR111##  Cl SO.sub.3 H                                                                         H                                                                                  ##STR112##                                                                               Reddish yellow                          50                                                                                   ##STR113##  Cl SO.sub.3 H                                                                         H                                                                                  ##STR114##                                                                               Reddish yellow                          51                                                                                   ##STR115##  Cl SO.sub.3 H                                                                         H                                                                                  ##STR116##                                                                               Reddish yellow                          52                                                                                   ##STR117##  Cl H   H                                                                                  ##STR118##                                                                               Reddish yellow                          53                                                                                   ##STR119##  Cl H   H                                                                                  ##STR120##                                                                               Reddish yellow                          54                                                                                   ##STR121##  Cl SO.sub.3 H                                                                         H                                                                                  ##STR122##                                                                               Reddish yellow                          55                                                                                   ##STR123##  Cl SO.sub.3 H                                                                         H                                                                                  ##STR124##                                                                               Reddish yellow                          56                                                                                   ##STR125##  Cl SO.sub.3 H                                                                         H                                                                                  ##STR126##                                                                               Reddish  yellow                         __________________________________________________________________________

EXAMPLE 57

41.6 g of the condensation product of 1,4-diaminobenzene-2,5-disulfonic acid and cyanuric chloride were diazotized in 500 ml of ice-water in the presence of hydrochloric acid and admixed with 24.2 g of 3-(3-methylimidazol-1-ylium)J-4-methyl-6-hydroxypyrid-2-one hydrochloride. The coupling was completed by raising the pH to 6-7. Then 9.4 g (0.05 mol) of 1,2-diaminobenzene-3-sulfonic acid, dissolved under neutral conditions in 200 ml of water, were added, and the mixture was stirred at pH 6-7 and 40°-45° C. for 2 hours. After the reaction had ended, sodium chloride was added to salt out the dye of the formula ##STR127## which was filtered off. It dyes cotton in a brilliant reddish yellow shade having a good light fastness and good wet fastness properties.

The same method is used to obtain the dyes listed in Table 4.

                                      TABLE 4                                      __________________________________________________________________________      ##STR128##                                                                    Example                                         Hue on                         No.  L.sup.1               Hal                                                                               A   L.sup.2                                                                           L.sup.3    cotton                         __________________________________________________________________________     58                                                                                   ##STR129##           Cl SO.sub.3 H                                                                         H                                                                                  ##STR130##                                                                               Greenish yellow                59                                                                                   ##STR131##           Cl H   H                                                                                  ##STR132##                                                                               Greenish yellow                60                                                                                   ##STR133##           Cl SO.sub.3 H                                                                         H                                                                                  ##STR134##                                                                               Greenish yellow                61                                                                                   ##STR135##           Cl H   H                                                                                  ##STR136##                                                                               Greenish yellow                62                                                                                   ##STR137##           Cl H   H                                                                                  ##STR138##                                                                               Greenish yellow                63                                                                                   ##STR139##           Cl SO.sub.3 H                                                                         H                                                                                  ##STR140##                                                                               Greenish yellow                64                                                                                   ##STR141##           Cl H   H                                                                                  ##STR142##                                                                               Greenish yellow                65                                                                                   ##STR143##           Cl SO.sub.3 H                                                                         H                                                                                  ##STR144##                                                                               Greenish yellow                66                                                                                   ##STR145##           Cl H   H                                                                                  ##STR146##                                                                               Greenish yellow                __________________________________________________________________________

EXAMPLE 67

17.3 g (0.1 mol) of aniline-3-sulfonic acid were dissolved in 200 ml of water at pH 7 and admixed with a suspension of 18.5 g (0.1 mol) of cyanuric chloride in 200 ml of ice-water. Once free amino groups were no longer detectable, the mixture was filtered. The filtrate was admixed with a neutral solution of 2.02 g (0.1 mol) of 1-(N-methylaminomethyl)-3-aminobenzene-4-sulfonic acid in 300 ml of water, the mixture was stirred at 30° C. and pH 8.5-9 for 2 hours.

The secondary condensation product obtained was diazotized at 0°-5° C. in the presence of hydrochloric acid and admixed with 24.2 g (0.1 mol) of 3-(3-methylimidazol-1-ylium)-4-methyl-6-hydroxypyrid-2-one hydrochloride. The coupling was completed by raising the pH to 6-7. Sodium chloride was added to the resulting suspension to salt out the dye of the formula ##STR147## which was filtered off. It dyes cotton in a brilliant greenish yellow shade having a good light fastness and good wet fastness properties.

EXAMPLE 68

To 25.7 g (0.1 mol) of the hydrochloric acid diazonium salt of the condensation product of 5-chloro-2,4,6-trifluoropyrimidine and 1,3-diaminobenzene-4,6-disulfonic acid were added at 0°-5° C. 24.3 g (0.1 mol) of 3-(3-methylimidazol-1-ylium)-4-methyl-6-hydroxypyrid-2-one hydrochloride. Sodium bicarbonate was added to complete the coupling at pH 6-7. The dye obtained had the formula ##STR148## and was precipitated with sodium chloride. It dyes cotton sin a brilliant greenish yellow shade which has a good light fastness and good wet fastness properties. 

We claim:
 1. A reactive dye of the formula I ##STR149## where n is 1 or 2,X isin case a), when n is 1, a radical of the formula IIa, IIB or IIc ##STR150## where R¹ is hydrogen or C₁ -C₄ -alkyl and Hal is fluorine or chlorine; or in case b), when n is 2, a radical of the above-mentioned formula IIa, L¹ is:in case a), when n is 1 and X is a radical of the formula IIb or IIc, fluorine, chlorine, C₁ -C₄ -alkoxy or phenoxy; or in case b), when n is 1 and X is a radical of the formula IIa, C₁ -C₄ -alkyl, phenyl, or phenyl monosubstituted or disubstituted by hydroxysulfonyl, vinylsulfonyl or the radical

    --SO.sub.2 --C.sub.2 H.sub.4 --Z,

where Z is a group which is detachable under alkaline reaction conditions; orin case c), when n is 2 and X is a radical of the formula IIa, is selected from the group consisting of phenylene, biphenylene, stilbenediyl and ureylenebisphenyl, each of which is substituted by one or two hydroxysulfonyl groups, D is the radical of an aniline or aminonaphthalene diazo component which has at least one hydroxysulfonyl group, L² is hydrogen, C₁ -C₈ -alkyl, or C₂ -C₈ -alkyl which is substituted by hydroxyl and/or interrupted by one or two oxygen atoms which form an ether grouping; L³ is unsubstituted or substituted pyrrolium, pyrazolium, imidazolium, oxazolium, isoxazolium, thiazolium, isothiazolium, triazolium, oxadiazolium, thiadiazolium, pyridinium, pyridazinium, pyrimidinium or pyrazinium, wherein said substituents are selected from the group consisting of C₁ -C₁₈ -alkyl and carboxyl; and L⁴ is hydrogen or C₁ -C₄ -alkyl, with the proviso that the number of hydroxysulfonyl groups in the molecule exceeds that of the cationic groups by at least one.
 2. A reactive dye as claimed in claim 1, wherein X is a radical of the formula IIa or IIb and L¹ in case a), when n is 1 and X is a radical of the formula IIb, is chlorine, orin case b), when n is 1 and X is a radical of the formula IIa, is C₁ -C₄ -alkyl, phenyl or phenyl monosubstituted or disubstituted by hydroxysulfonyl, vinylsulfonyl or the radical

    --SO.sub.2 --C.sub.2 H.sub.4 --Z

where Z is a group which is detachable under alkaline reaction conditions, or in case c), when n is 2 and X is a radical of the formula IIa, is phenylene, biphenylene, stilbenediyl or ureylenebisphenyl, each of which is substituted by one or two hydroxysulfonyl groups.
 3. A reactive dye as claimed in claim 1, wherein D is the radical of an aniline diazo component which has one or two hydroxysulfonyl groups.
 4. A reactive dye as claimed in claim 1 of the formula Ia ##STR151## where n, R¹, Hal, L³ and L⁴ are each as defined in claim 6,L² is hydrogen or C₁ -C₄ -alkyl, A is hydrogen or hydroxysulfonyl and L¹, when n is 1, is C₁ -C₄ -alkyl, phenyl or phenyl monosubstituted or disubstituted by hydroxysulfonyl, vinylsulfonyl or the radical

    --SO.sub.2 --C.sub.2 H.sub.4 --Z,

where Z is a group which is detachable under alkaline reaction conditions, or, when n is 2, is mono- or dihydroxysulfonylphenylene, mono- or dihydroxysulfonylbiphenylene, mono- or dihydroxysulfonylstilbenediyl or mono- or dihydroxysulfonyl-4,4'-ureylenebisphenyl.
 5. A reactive dye according to claim 4 wherein L³ is selected from the group consisting of pyridinium, pyridinium substituted by carboxylate anion, imidazolium, and imidazolium substituted by up to four C₁ -C₄ -alkyl groupings.
 6. A method for dyeing or printing hydroxyl- or nitrogen-containing substrates comprising contacting said substrate with a reactive dye according to claim
 1. 